Simultaneous quantification of short-, medium-, and long-chain chlorinated paraffins (CPs) in environmental matrices is challenging and has received much attention from environmental chemists. In this study, ammonium-chloride-enhanced liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) was developed for the first time to quantify CPs in sediments and aqueous samples. Three ionization sources, including atmospheric pressure chemical ionization (APCI), electrospray ionization (ESI), and thermal-assisted-ESI, were employed to examine the performance of ammonium chloride as the chloride ion supply reagent in comparison with traditional chloride ion supply reagent, dichloromethane. Ammonium chloride can be easily used with reversed-phase liquid chromatography (LC), whereas dichloromethane is not compatible with aqueous LC mobile phase. Furthermore, other anion-supply reagents, such as ammonium formate, ammonium acetate, and ammonium bromide, were also tested. It was concluded that the adducts of the CPs with the anions were reversible and could partially dissociate into deprotonated CP ions. The yield of deprotonated CP ions was associated with the gas-phase basicity of the deprotonated CP ions and the corresponding anions. Furthermore, collision-induced dissociation curves were drawn to quantify the stability of anionic CP adducts. The ammonium-chloride-enhanced LC-HRMS was further employed for identifying CPs in sediment samples and coupled with an online SPE method for detecting CPs in aqueous samples. This study may significantly contribute to the qualification and quantification of CPs in environmental matrices.

Chemical compositions of fog and rain water were measured between July 2017 and September 2018 at Sejila Mountain, southeast Tibet, where fog events frequently occurred in original fir forests at altitude 3950 m. Fog water samples were collected using a Caltech Active Strand Cloud Collector (CASCC), and rain samples were collected using a precipitation gauge. Differences were observed between fog water and rain composition for most analyzed ions. Ion abundance in fog water was Ca²⁺ > Cl⁻ > Na⁺ > SO₄²⁻ > Mg²⁺ > NH₄⁺ >K⁺ > NO₃⁻ whereas an order of Ca²⁺ > Na⁺ > Cl⁻ > Mg²⁺ > SO₄²⁻ > NO₃⁻ > K⁺ > NH₄⁺ was observed for rain water. All ion concentrations were higher in fog water than in rain water. Additionally, Ca²⁺ was the dominant cation in both fog and rain samples, accounting for more than half of all measured cations. NH₄⁺ and SO₄²⁻ concentrations were notable for being higher in fog than rain water when compared with other ions. For trace elements, Al, As, Mn and Se were the most abundant elements in fog water; only Al and As were detected in rain water. Seventy-two hour back-trajectory analysis showed that air masses during fog and/or rain events mainly came from the south of Sejila Mountain. Spearman correlation analysis and source contribution calculations indicated that both marine and terrestrial sources contributed to the observed ion concentrations. Considering the higher concentrations of NH₄⁺ and higher ratio of NH₄⁺/NO₃⁻ measured in fog than in rain, we suggest that quantification of fog nitrogen deposition and its ecological effect in this area should be given more attention.

Thiocyanate (SCN⁻)-based autotrophic denitrification (AD) has recently been demonstrated as a promising technology that could be integrated with anaerobic ammonium oxidation (Anammox) to achieve simultaneous removal of nitrogen and SCN⁻. However, there is still a lack of a complete SCN⁻-based AD model, and the potential microbial competition/synergy between AD bacteria and Anammox bacteria under different operating conditions remains unknown, which significantly hinders the possible application of coupling SCN⁻-based AD with Anammox. To this end, a complete SCN⁻-based AD model was firstly developed and reliably calibrated/validated using experimental datasets. The obtained SCN⁻-based AD model was then integrated with the well-established Anammox model and satisfactorily verified with experimental data from a system coupling AD with Anammox. The integrated model was lastly applied to investigate the impacts of influent NH₄⁺-N/NO₂⁻-N ratio and SCN⁻ concentration on the steady-state microbial composition as well as the removal of nitrogen and SCN⁻. The results showed that the NH₄⁺-N/NO₂⁻-N ratio in the presence of a certain SCN⁻ level should be controlled at a proper value so that the maximum synergy between AD bacteria and Anammox bacteria could be achieved while their competition for NO₂⁻ would be minimized. For the simultaneous maximum removal (>95%) of nitrogen and SCN⁻, there existed a negative relationship between the influent SCN⁻ concentration and the optimal NH₄⁺-N/NO₂⁻-N ratio needed.

Endocrine disrupting chemicals (EDCs) are substances which disrupt normal functioning of the endocrine system by interfering with hormone regulated physiological pathways. Aquatic environments provide the ultimate reservoir for many EDCs as they enter rivers and the ocean via effluent discharges and accumulate in sediments. One EDC widely dispersed in municipal wastewater effluent discharges is 17α-ethynylestradiol (EE2), which is one of the most widely prescribed medicines. EE2 is a bio-active estrogen employed in the majority of oral contraceptive pill formulations. As evidence of the health risks posed by EDCs mount, there is an urgent need to improve diagnostic tools for monitoring the effects of pollutants. As the cost of high throughput sequencing (HTS) diminishes, transcriptional profiling of an organism in response to EDC perturbation presents a cost-effective way of screening a wide range of endocrine responses. Coastal pelagic filter feeding fish species analyzed using HTS provide an excellent tool for EDC risk assessment in the marine environment. Unfortunately, there are limited genome sequence data and annotation for many of these species including Pacific sardine (Sardinops sagax) and chub mackerel (Scomber japonicus), which limits the utility of molecular tools such as HTS to interrogate the effects of endocrine disruption. In this study, we carried out RNA sequencing (RNAseq) of liver RNA harvested from wild sardine and mackerel exposed for 5 h under laboratory conditions to a concentration of 12.5 pM EE2 in the tank water. We developed an analytical framework for transcriptomic analyses of species with limited genomic information. EE2 exposure altered expression patterns of key genes involved in important metabolic and physiological processes. The systems approach presented here provides a powerful tool for obtaining a comprehensive picture of endocrine disruption in aquatic organisms.

Measurements of biological responses on living organisms are essential in aquatic biomonitoring. In freshwaters, Dreissena polymorpha is an invasive bivalve commonly used in ecotoxicological studies and considered as a model organism. However, D. polymorpha abundances are declining while another species colonizes most of the freshwaters: Dreissena rostriformis bugensis. This species has already been studied in ecophysiology but there is still a lack of data concerning its responses to stressors before its use as a bioindicator of environmental pollution. This study aims to compare the responses of the two species exposed to metal stress. Responses at different levels of biological organization were targeted with measurement of sub-cellular and individual biomarkers following an exposure of up to 7 days to cadmium at 10 μg.L−1. At the individual level, the scope for growth (SFG) was measured. It corresponds to the energy allocated to growth and reproduction. D. polymorpha exhibits variations in biomarker measurements as well as in the SFG in presence of Cd. D. r. bugensis shows no variation in its responses at the different targeted levels. According to the present results, energy metabolism seems to have an essential role for these species when facing a metal stress. Different energy allocation strategies were evidenced between the two species, although the link with biochemical biomarkers is more evident for D. polymorpha than for D. r. bugensis.

Phagocytosis suppression induced by nanoparticles (NPs) exposure is increasingly reported in marine species. However, the mechanisms underlying this impact remain poorly understood. In order to improve our present understanding of the immunotoxicity of NPs, acute (96 h) TiO2 NP exposure and rescue trials via exogenous supply of Ca2+ were performed in the blood clam, Tegillarca granosa. The results show that the phagocytosis rate, cell viability, and intracellular Ca2+ concentration of haemocytes were significantly suppressed, whereas the intracellular ROS concentration of haemocytes significantly increased upon nTiO2 exposure. Exposure to nTiO2 also led to the significant downregulation of Caspase-3, Caspase-6, apoptosis regulator Bcl-2, Bcl-2-associated X, calmodulin kinase II, and calmodulin kinase kinase II. Furthermore, the toxic impacts of nTiO2 were partially mitigated by the addition of exogenous Ca2+, as indicated by the recovery tendency in almost all the measured parameters. The present study indicates that Ca2+ signaling could be one of the key pathways through which nTiO2 attacks phagocytosis.

Pyrethroids are a class of widely-used insecticides that can be transported from terrestrial applications to aquatic systems via runoff and tend to sorb to organic carbon in sediments. Pyrethroid occurrence is detrimental to stream ecosystems due to toxicity to sediment-dwelling invertebrates which are particularly at risk of pyrethroid exposure in urban streams. In this work, 49 streams located in watersheds in the northeastern United States were surveyed for nine current-use pyrethroids using two extraction methods. Total sediment concentrations were determined by exhaustive chemical extraction, while bioaccessible concentrations were determined by single-point Tenax extraction. Total and bioaccessible pyrethroid concentrations were detected in 76% and 67% of the sites, and the average sum of pyrethroids was 232 ng/g organic carbon (OC) for total and 43.8 ng/g OC for bioaccessible pyrethroids. Bifenthrin was the most commonly detected pyrethroid in streambed sediments. Sediment toxicity was assessed using 10-d Hyalella azteca bioassays, and 28% and 15% of sediments caused a decrease in H. azteca biomass and survival, respectively. A temperature-based focused toxicity identification evaluation was used to assess pyrethroids as the causal factor for toxicity. The concentrations of pyrethroids was only weakly correlated with the degree of urban land use. Sediment toxicity was predicted by total and bioaccessible pyrethroid concentrations expressed as toxic units. This work suggests that bioaccessibility-based methods, such as Tenax extraction, can be a valuable tool in assessing sediment toxicity.

Measurements of speciated atmospheric mercury play a key role in identifying mercury behavior in the atmosphere. In this study, we measured speciated atmospheric mercury, including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM), and particulate bound mercury (PBM) (<2.5 μm), in 2015 and 2016 at an urban site in Beijing, China. The mean concentrations of GEM, RGM, and PBM were 4.70 ± 3.53 ng m−3, 18.47 ± 22.27 pg m−3, and 85.18 ± 95.34 pg m−3, respectively. The concentration of PM2.5 significantly affected the distribution of reactive mercury between the gaseous and particulate phases. With the raising of PM2.5 levels, PBM concentrations increased, on the contrary, the concentrations of RGM decreased gradually. The mean concentration of PBM during air-pollution events was more than three times that during clear days. During days with air pollution, the relative humidity significantly affected the gas-particle partitioning of reactive mercury. The linear relationships between gas-particle partitioning coefficient and meteorological factors (air temperature and relative humidity) were obtained over the four seasons. The data also showed that the gas-particle partitioning coefficient of reactive mercury was related to particle composition (e.g., Cl−, BC). The data present in this paper suggested the influence of anthropogenic emissions on reactive mercury in Beijing urban. And the findings will contribute to understand the gas-particle partitioning of reactive mercury and its influencing factors with complex urban pollution.

Struvite recovered from swine wastewater can be used as a good slow release fertilizer. Nevertheless, the presence of heavy metals would be easily precipitated with struvite and increase the ecological risk for its agricultural use. This paper investigated the possibility of using process variables for heavy metal (Cu2+, Zn2+ and Cr3+) minimization during struvite crystallization in swine wastewater. The heavy metal content, effect ratios (ER) of the citric acid concentration under varying conditions were tested and their SEM, EDS and XRD patterns were compared for morphology analysis. The results show that an increase in pH decreased the content of Cu, Zn and Cr in recovered precipitates. Heavy metal content in the precipitates increased markedly with their initial concentrations in the solution. The effect ratio calculation indicates that Cr has the strongest co-precipitation potential, followed by Zn and Cu. An increase in citric acid concentration reduced the heavy metal removal efficiency (14.3, 27.7 and 28.1% for Cu, Zn and Cr, respectively) but did not decrease their content in struvite precipitates. What is more, increase of total ammonia nitrogen (TAN) to soluble phosphate molar ratio significantly decreased Cu, Zn removal efficiency (52.2 and 50% respectively), while Mg:PO4P molar ratio had much less effect.

There are global concerns about heavy metal (HM) contamination in soils, which in turn has produced an increased demand for soil remediation. Biochar has been widely documented to effectively immobilize metals in contaminated soils and has received increasing attention for use in soil remediation. Here, we review recent progresses in understanding metal-biochar interactions in soils, potential risks associated with biochar amendment, and application of biochar in soil remediation in China. These recent studies indicate that: (1) the remediation effect depends on the characteristics of both biochar and soil and their interactions; (2) biochar applications could decrease the mobility/bioavailability of HMs in soils and HM accumulation in plants; and (3) despite its advantages, biochar applications could pose ecological and health risks, e.g., by releasing toxic substances into soils or by inhalation of biochar dust. Research gaps still exist in the development of practical methods for preparing and applying different biochars that target specific HMs. In the future, the long term effects and security of biochar applications on soil remediation, soil organisms and plant growth need to be considered.